Constructing extrinsic oxygen vacancy on the surface of photocatalyst as CO2 and electrons reservoirs to improve photocatalytic CO2 reduction activity.

Constructing own oxygen vacancies in the photocatalysts is a very promising method to improve their photocatalytic CO2 reduction activity. However, some catalysts have excellent stabilities, making it difficult for them to construct their own oxygen vacancies. To simplify the above difficulty of stable photocatalysts, constructing extrinsic oxygen vacancies on their surface as a novel idea is proposed. Here, a stable TiO2 nanosheet is chosen as a research object, we uniformly deposited BiOCl quantum dots on their surface via a simple adsorption-deposition method. It is found that BiOCl quantum dots are able to simultaneously self-transform into defective BiOCl with many oxygen vacancies when the photocatalyst is performed photocatalytic CO2 reduction. These extrinsic oxygen vacancies can act as "CO2 and photo-generated electrons reservoirs" to improve CO2 capture and accelerate the separation of photogenerated electrons and holes. For the above reasons, the modified TiO2 showed obvious enhancement of photocatalytic CO2 reduction compared to pristine TiO2 and BiOCl. This work may open a new avenue to broaden the use of oxygen vacancies in the process of photocatalytic CO2 reduction.

Architecture Design and Catalytic Activity: Non-Noble Bimetallic CoFe/fe3 O4 Core-Shell Structures for CO2 Hydrogenation.

Non-noble metal catalysts now play a key role in promoting efficiently and economically catalytic reduction of CO2 into clean energy, which is an important strategy to ameliorate global warming and resource shortage issues. Here, a non-noble bimetallic catalyst of CoFe/Fe3 O4 nanoparticles is successfully designed with a core-shell structure that is well dispersed on the defect-rich carbon substrate for the hydrogenation of CO2 under mild conditions. The catalysts exhibit a high CO2 conversion activity with the rate of 30% and CO selectivity of 99%, and extremely robust stability without performance decay over 90 h in the reverse water gas shift reaction process. Notably, it is found that the reversible exsolution/dissolution of cobalt in the Fe3 O4 shell will lead to a dynamic and reversible deactivation/regeneration of the catalysts, accompanying by shell thickness breathing during the repeated cycles, via atomic structure study of the catalysts at different reaction stages. Combined with density functional theory calculations, the catalytic activity reversible regeneration mechanism is proposed. This work reveals the structure-property relationship for rational structure design of the advanced non-noble metallic catalyst materials with much improved performance.

Living Atomically Dispersed Cu Ultrathin TiO2 Nanosheet CO2 Reduction Photocatalyst.

Supported atomically dispersed metals are proving to be efficacious photocatalysts for CO2 reduction to solar fuels. While being atom efficient, they suffer from being noble, rare, and costly (Pt, Pd, Au, Ag, Rh) and lacking in long-term stability. Herein, all of these problems are solved with the discovery that atomically dispersed Cu supported on ultrathin TiO2 nanosheets can photocatalytically reduce an aqueous solution of CO2 to CO. The atomically dispersed Cu can be recycled in a straightforward procedure when they become oxidatively deactivated. This advance bodes well for the development of a solar fuels technology founded on abundant, low-cost, nontoxic, atomically dispersed metal photocatalysts.